Art of manufacturing dry wall taping and finishing compounds with a nitrogenous-modified amylaceous binder

ABSTRACT

Urea is combined with a gelatinized amylaceous material using water in an amount less than 20 percent of the total mix, and the mixture is subsequently heated to obtain a binder for use in a dry wall finishing compound.

United States Patent [191 Cnm misford [11] 3,725,324 51 Apr; 3,1973

[54] ART OF MANUFACTURING DRY WALL TAPING AND FINISHING COMPOUNDS WITH A NITROGENOUS- MODIFIED AMYLACEOUS BINDER [75] Inventor: Robert G. Cummisford, Brookfield,

Wis.

[73] Assignee: Krause Milling Company, Milwaukee, Wis.

[22] Filed: May 27, 1971 [21] Appl. No.: 147,644

[52] U.S. CI. ..260/17.4 ST, 106/210, 106/214 [51] Int. Cl. ..C08b 25/02, C08d 9/06 [58] Field of Search ..260/17.4 ST, 17.3; 106/210,

Primary Examiner-Harold D. Anderson Assistant Examiner-Edward Woodberry Att0rneyMorsell & Morsell [57] ABSTRACT Urea is combined with a gelatinized amylaceous material using water in an amount less than 20 percent of the total mix, and vthe mixture is subsequently heated'to obtain a binder for use in a dry wall finishing compound.

19 Claims, No Drawings ART OF MANUFACTURING DRY WALL TAPING AND FINISHING COMPOUNDS WITH A NITROGENOUS-MODIFIEI) AMYLACEOUS BINDER BACKGROUND OF THE INVENTION 1. Field of the Invention The compound of the present invention is particularly useful as a dry wall joint cement used in the taping of dry wall joints or as a dry wall finish, and the improved binder portion is satisfactory for the preparation of acoustic finishes and other surface finishes for application to walls.

2. Description of the Prior Art With the use of gypsum drywall as a wall surfacing material in construction projects certain adhesive fillers are used to close and fill the joints between adjoining pieces of dry wall. These same adhesive fillers and others with slightly changed'formulations are also used to give novel textured finishes to the otherwise smooth dry wall surface.

In the past dry wall finishes have been formulated with a variety of binders and an even wider variety of inorganic filler pigments. The binders most often used have been casein, soy protein, pregelatinized oxidized starch, polyvinyl alcohol and polyvinyl acetate either as a spray dried powder or water emulsion. The inorganic fillers used having included limestone flour, mica, talc,

clays, asbestos, titanium dioxide, calcined clays and others common to adhesive and paint technology.

Inasmuch as the present invention relates primarily to a method which employs a novel binder, the shortcomings of the common binders will be listed. Casein has need for alkaline solubilizing salts which must be included in the formulation; the dry powder has limited storage stability due to decomposition or inactivation of these solubilizers. Casein also is difficult to preserve against microbiologicalattack particularly after the powder has been admixed with water prior to use. A. S.T.M. standard specification C 475-64 requires no putrefaction in less than 4 days. Preservative levels of 0.4 percent and greater are commonly used with casein to achieve this standard of performance. The amount of casein in such formulations usuallyis greater than 5 -percent, in the range of 6-7 percent for a joint compound.

The soy proteins have the same disadvantages as casein. In addition they have a tendency to form a very hard surface upon drying, making them difficult to work with and to paint. Furthermore, they are slow to dissolve and require a high pH for solution. The use of soy protein in dry wall finishes has diminished because of these disadvantages.

. The pregelatinized oxidized starches haveas disadvantages a very soft characteristic upon drying and a tendency for the adhesive effectiveness to decrease as water demand decreases causing the formulator to choose between adhesive performance and workability during application. As a result these materials are commonly used as partial replacement for a more expensive binder to lower the cost of a binder system.

Polyvinyl alcohol is seldom used as the sole binder in dry wall finishes because of its sensitivity to other materials, its cost, and a tendency to have unsatisfactory application performance. It is most often used as a minor part of a binder system to impart special properties to the overall dry wall finish. Polyvinyl acetate as a spray dried powder has the disadvantages of high cost, poor workability and poor low temperature performance. By using it with other binder components these difficulties can be overcome. As an emulsion it can be used in ready-to-use wet finishes, but these have shipping and storage problems. By involved pre-mixing of the emulsion on a carrier material the emulsion can be used in a semi-dry mix, but this approach has not gained wide acceptability.

While the inclusion of urea into amylaceous adhesives to improve plasticity or flexibility is old, it is new to combine the amylaceous material and urea and subsequently heat the mixture to obtain a pregelatinized amylaceous material containing urea, except for British Pat. No. 1,127,198 in which a similar product is used as a ruminant feed.

In most cases of urea addition to amylaceous adhesives, the urea is added during or after cooking. The addition of urea to a pregelatinized cereal flour does not give the same result as does the present method where heating is performed in the presence of urea and in the presence of gelatinized material. Particularly, the workability and crack resistance suffer.

The patents which mention combination of urea and starch to form carbamates are similar to the present invention, but I do not form carbamate to any significant degree. Formation of carbamate requires the evolution of a mole of ammonia for each mole of carbamate formed. Nitrogen analysis of my products indicates little if any loss of nitrogen as ammonia during processing.

In the area of dry wall finish patents Gogek, U. S. Pat. No. 3,411,926, requires a blend of gelatinized and ungelatinized starch. In. comparing the binder of my invention with the binder of Gogek, I find the only similarity in the fact that both use amylaceous starting materials. He specifies an oxidized starch, my binder is not oxidized. Further, the test data on my binder comf pared with data given in his examples indicate that while his adhesion increased as the binder was in.- creased from 1 to 5 percent, the crack resistance decreased. In testing my binder I have found that both adhesion and crack resistance increase as the binder is increased from 3 to5 percennThe materials claimed as binders are obviously different.

Protzman U.S. Pat. No. 3,l37,592 uses 22 percent plasticizer and at least a 50 C. adiabatic temperature rise during extrusion cooking. In his teachings urea is equated with water as a plasticizer. Protzman has a general extruded starch patent covering a special set of operating conditions wherein the temperature is raised at least 50 C. adiabatically.

SUMMARY OF THE INVENTION With the present invention, to obtain a binder for use ina dry wall taping and finishing compound, a cereal grain or an amylaceous fraction thereof is gelatinized in the presence of a non-volatile starch plasticizer such as urea or with another nitrogen compound related to urea. Alternatively, a pregelatinized cereal grain or amylaceous fraction thereof is admixed with the plasticizer and heated to effect an association of the plasticizer with the amylaceous material. With the present invention the binder portion of the dry wall finishing material is new and novel, and this comprises a minor portion of the joint cement. Any of amultitude of combinations of possible fillers, pigments, and other additives can be used for the major portion of the joint cement depending on the formulators purpose.

A general object of the invention is to provide a dry wall compound for joint or finishing use which gives improved functional characteristics as compared with those materials presently available for a similar purpose in that the compound has excellent bonding qualities, resistance to cracking and shrinkage, and resistance to putrefaction.

A further objectof the invention is to provide a dry wall compound including a novel cereal-based binder.

A still further object of the invention is to provide an improved compound for dry wall use in which both workability and crack resistance are improved coincidentally.

- DESCRIPTION OF THE PREFERRED EMBODIMENT The binder of the present invention is a cereal grain or an amylaceous fraction thereof which is gelatinized in the presence of a non-volatile starch plasticizer such as urea or a nitrogen compound related to urea using water in an amount less than percent of the total mix with a heating step being performed in the presence of the urea and in the presence of the gelatinized material to bring the temperature to between 115 C. and 180 C. The nitrogen compound is of the family containing .the chemical grouping where X is O, S, or NH, and where R is H or CH and where R is H or CH and is present in the amount of 3 percent to 20 percent based on the weight of the flour. A specific series of compounds having this grouping would be of the general formula (R,R N) C:X where R and R are H or CH and X is O or S.

Alternatively, the binder is a pregelatinized cereal grain or amylaceous fraction thereof intimately admixed with the plasticizer and then heated to bring the temperature to between 75 C. and 180 C. to effect an association of the plasticizer with the amylaceous material. A preferred method for simultaneously gelatinizing and heating involves extrusion cooking of the urea treated amylaceous material.

The gelatinization may be performed by any well known method and requires heating the starch in the flour, corn starch, grain sorghum flour, milo meal and presence of water to the gelatinization temperature of the starch. Where extrusion-cooking is employed the starch product is extruded into the atmosphere to provide an area of reduced pressure. The extrusion process is generally conducted at a temperature of between 115 C. and 177 C. at a pressure of between 100 and 350 psi, or greater. Where the extrusion process is employed the gelatinization and heating are done simultaneously in the presence of the urea and it is to be understood that when gelatinization and heating are recited in the claims that gelatinization and heating may be performed simultaneously, as in an extrusioncooking process, or gelatinization may be performed first and heating later, it being essential that heating be done in the presence of both gelatinized amylaceous material and the urea or other nitrogen compound.

wheat flour.

The following are examples of nitrogen compounds that may be used: urea, (H N) C:O; thiourea, (H N) C: S; guanidine, (H N) C:NH; biurea, [HN(H N C:O]

biuret, HN[(H N)CZO]z; dicyandiamide, NCNH(H N)C:NH.

The urea treated binder may be used in various joint compound formulations as follows, the percentages beirig based on the total weight of the joint compound:

Part 1 Urea-modified cereal binder 3 percent percent Part 2 Filler and pigment materials, together with such other additional materials as may be desired to provide smoother spreading, ease of mixing to control drying rate, shrinkage and to serve as a buffer to adjust the pH or to serve as a pigment dispersant. The basic ingredients of the filler may include mica, asbestos, and limestone, or calcium carbonate, together with such other materials as may be desired percent 97 percent Various of such other materials may be employed in Part 2 above as are well known in wallboard finishing compounds, and such materials may be employed in varying percentages. For convenience, Part 2 will be referred to in the claims merely as filler material. The formulation for Part 2, however, can be varied over a wide latitude depending upon the particular characteristics desired. While the use of some gummy substance to obtain smoother spreading is highly desirable, it is not absolutely essential. The following may be used for this purpose, among other things: hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, guar gum, alginates, gum arabic, gum tragacanth. While not critical, it is also desirable to employ-a small amount of a buffer which also serves to adjust thepH and which is a pigment dispersant. This may be sodium carbonate, sodium tripolyphosphate, sodium hexametaphosphate, sodium orthophosphate, sodium sesquicarbonate. A small amount of a plasticizer such as N-Butyl phthalate or sodium acetate may also be employed in Part 2. The remainder of Part 2 comprises filler and pigment materials which may be one or more of the following: limestone, clay, mica, asbestos, calcium carbonate.

The following examples illustrate the invention more specifically:

EXAMPLE 1 18 grams of a bleached extruded corn flour was admixed with 2 grams of urea and the mixture was heated in an oven for 2 hours at 100 C. When .cooled the Kaolin clay (Kaolex CW) Calcium carbonate (No. 1 white) When mixed with water in a ratio of 100 parts joint compound to 65 parts water by weight an easy spreading joint compound resulted. The bond between embedded tape and the joint compound upon drying was 100 percent, only slight evidence of cracking was apparent. When bleached extruded corn flour which was not urea treated was used as a binder, a sticky hardworking joint compound with severe cracking upon drying resulted. The viscosities of the different materials used as binder in the above examples, when not urea treated, were 10 percent cold paste: 208 cps (Brookfield); and when urea treated, were 10 percent cold paste: 1320 cps (Brookfield). The fact that the higher viscosity material worked better as a joint compound binder is completely contrary to what is observed with common binders.

EXAMPLE 2 The urea-treated binder of Example 1 was used in another joint compound formulation in which 4 percent urea-treated product and 1 percent polyvinyl alcohol were used as a binder system. An easyworkin'g joint compound with crack resistance resulted. This formulation was:

Urea-treated binder of Example 1 4% Polyvinyl alcohol 1% Binder HEC 15000) 0.1% Sodium carbonate 0.5% N-Butyl Phthalate 0.3% Pigment Asbestos (7RF-9) 7% and Mica (3X) filler Mica (4X) 5% materials Clay (Kaolex CW) Limestone (No. 1 white) 67% This formulation met all ASTM C 475-64 requirements; it passed the requirement for putrefaction even though there was no preservative present. This compound, when admixed with water, was also usable after two freeze-thaw cycles.

EXAMPLE 3 A series of pregelatinized products were prepared by extrusion-cooking of a mixture of yellow corn meal, 10 percent urea and 17 percent water based on weight of corn meal, in a laboratory plastics extruder under conditions giving the following viscosities:

Brookfield Viscosity. cps. Cold paste Hot paste 10% 10% Sample A 510 221 Sample B 1560 630 Sample C 2720 3250 Sample D 1530 4400 Sample E 1650 3280 Sample F 1700 3930 EXAMPLE 4 An extruded binder was prepared on a commercial size cooker-extruder using yellow corn flour, 0.08 percent benzoyl peroxide bleach and 10 percent urea by weight of flour with conditions during extrusion such that'the following viscosities resulted:

Brookfield Viscosity, cps. Cold paste 10% Hot paste 10% A 320 176 B 284 Both of these binders were suitable in formulations listed under Example 1. Reducing binder level to 4 percent resulted in acceptable joint-compounds. Reducing the binder to 3 percent gave joint compounds having poor workability.

EXAMPLE 5 EXAMPLE 6 Six extruded products using different nitrogen additives were made on a laboratory extruder with a maximum temperature of C. with coarse corn meal, 18 percent moisture and 10 percent nitrogen compound based ondry weight of corn meal. The'extrudate'was ground to all pass 80 mesh. These ground materials were used in formulation of Example 2. Results are shown in Table l.

TABLE I Nitrogen Cold. Hot Example Additive Paste Paste Cracking Bond 6a Urea 352 None Good 6b Thiourea 2230 2920 None Good 6c Guanidine (HC 1) 134 107 None Good 6d Biurea 1 10 None Good 6e Biuret 264 192 None Good 61' Dicyandiamide 218 208 None Good The formulas for the above nitrogen additives are urea, (H N) C:O; thiourea, (H N) C:S; guanidine, (H N) C: NH; biurea, [NH(H N)C:(] biuret, HN[(H N)C:O] dicyandiamide, NCNH(H N)C:O. From these formulas the similarity of structure is obvious.

EXAMPLE 7 Joint compounds were formulated using a binder from Gogek U. S. Pat. No. 3,411,926, a partially gelatinized oxidized corn starch and binder from Example 4b. Formulation was the same as Example 1, except that the binder was varied from 5 percent to 3 percent with limestone flour making up the difference; Table 11 contains results of tests on these joint compounds, performed according to A.S.T.M. C 475-64 methods.

TABLE n nd Binder cc/l00gms Wedge Cracking Paper Wall k N P 3 g water, and, in certain instances, with the addition of aggggg 22 some 32 gg 4 gregate, and in the claims, where the term wallboard Gogek 65 Many Large & Small Good 5 Fail joint compound is used, it is to be understood that this Ex. 4b 68 None Good 3 Good EX 4b 68 None Good 4 Good 5 also comprehends compounds suitable for such Ex. 4b 68 None Good 5 Good fmlshes- What I claim is: These results emphasize the differences between prior A method 9? manufacturing wallboard J art cereal binders and the binder of this invention. p d Compnsmg the Steps of P p a bmder by combining a nitrogen compound with a gelatinized EXAMPLE 8 1O unoxidized amylaceous material using water in an A product was made by preparingthe binder using amount less than 20 percent of the total mix, and heatsecond clear wheat flour mixed with 10 percent urea mg the mixture to h the temphhathre to bhtweeh based on flour weight. Water was added to bring the and 180 C whhe the lgelahmzed h l moisture of the flour mix to 18 percent. This was exhhrogeh h h are ,h Present; h d hg a truded at a maximum temperature of 150 C. to give a mmohpfopomoh of the h major propomoh product with a cold paste Brookfield viscosity at 10 lolht compound the hhhogeh Compound percent solids of 262 cps. and a hot paste Brookfield bemg h h amouht of 3 9 perceht based 9 viscosity of l 150 cps. When used in the formulation of the W h amylaceohs matemh and hemg of the Example 2, the bond to the paper tape was 85-90 per- 20 famhy cohtalmhg the h l grouping cent rather than 95-100 percent as with corn based binders. Workability of this binder was judged to be tackier than the corn based binder demonstratin the t I wide difference in workability possible using the 3:2 :2 g g g h h where R1 18 H or CH3 and .techmque dlsclosedmthsteachmg' 2. A inethod as et forth in claim 1 in which the EXAMPLE 9 amylaceous material is cereal grain or an amylaceous fraction thereof.

3, A method as set forth in claim 1 in which the nitrogen compound is urea.

4. A method as set forth in claim 1 in which the nitrogen compound is of the general formula (R,R N) C:X where R and R are H or CH and X is O or S.

A binder was prepared using milo grits as a starting material. The-milo grits were blended with urea in a ratio of 9:1 andthe resulting mix brought to 18 percent water content.'This mix was extruded to give a product with 119 cps. Brookfield cold paste and an 87 cps. Brookfield hot paste. When used in the joint compound formulation of Example 2, bond and wedge cracking tree 0 nd i f the f mil contai 'n the were excellent. I my 3 h comp S 0 a y m g chemical grouping r EXAMPLE 10 Two binders were made from corn grits using different I levels of urea. These were extruded after adjusting to 40 where X is 0,8, or NH. 18 percent moisture at a temperature of 150 C. max- 6. A method as set forth in claim '1 in which the 5. A method as' set forth in claim 1 in which they 'imum. Table Illshows urea level, analytical data and nitrogen compound'is selected from the group compris- .test results on these binders used in joint compound ing the following: urea, guanidine, thiourea, biurea,

formulation from Example 2. I biuret, and dicyandiamide.

TABLE III Results using corn grlts and difierent urea levels Spreading Parts consistency, uren (Jold lIol Edge Wedge Howl Wnllen. H1O lurts corn grits by wt. paste paste crack crack tripe hoard 100 qms 10.... l 1133 234 Nm1 None Good," (l()()ll. ex 17 3 256 202 ;do do... do .do

The only difference in these two samples is the amount 7. A method as set forth in claim 1 in which the of water per 100 gms. joint compound needed to get amylaceous material lS selected from a group comprisspreading consistency. The lower cold viscosity binder ing corn flour, corn starch, gram sorghum flour, corn requires higher water addition to get comparable 65 mea 60m g mllomsal, mllO a and Whca! flourviscosity used in joint compound. 8. A method as set forth in claim 1 in which the It is well known that wallboard joint compounds are binder is 3.0 percent-10.0 percent of the total weight suitable as dry wall finishes, usually with the addition of of the joint compound, and wherein the filler is percent-97 percent of the total weight of the joint comwhere X is O, S, or NH and where R is H or CH and where R, is H or CH and a gelatinized unoxidiz ed amylaceous material, with the association of said mixture having been effected by heating to a temperature between 75 C and 180 C, the nitrogen compound being present in the amount of 3 percentpercent based upon the weight of the amylaceous material.

12. A wallboard joint compound as claimed in claim 11 in which the amylaceous material is cereal grain or an amylaceous fraction thereof.

13. A wallboard joint compound as claimed in claim 1 l in which the nitrogen compound is urea.

14. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is selected from a group comprising the following: urea, biurea, biuret, thiourea, guanidine, and dicyandiamide.

15 A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is of the general" formula (R,R N) C:X, where R and R are H or CH and X is O or S.

16. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is of the 'famil containing the chemical grouping where X is O, S, or NH.

17. A wallboard joint compound as claimed in claim 11 in which the amylaceous material is selected from the group comprising the following: corn flour, corn starch, grain sorghum flour, corn meal, cor'n grits, milo meal, milo grits, and wheat flour.

18. A wallboard joint compound as claimed in claim 11 in which the filler is percent-97 percent of the total weight of the joint compound, and in'which the binder is 3 percent-1O percent of the total weight of the joint compound.

19. A wallboard joint compound as claimed in claim 11 in which the binder includes a minor percentage of polyvinyl alcohol. 

2. A method as set forTh in claim 1 in which the amylaceous material is cereal grain or an amylaceous fraction thereof.
 3. A method as set forth in claim 1 in which the nitrogen compound is urea.
 4. A method as set forth in claim 1 in which the nitrogen compound is of the general formula (R1R2N)2C:X where R1 and R2 are H or CH3, and X is O or S.
 5. A method as set forth in claim 1 in which the nitrogen compound is of the family containing the chemical grouping
 6. A method as set forth in claim 1 in which the nitrogen compound is selected from the group comprising the following: urea, guanidine, thiourea, biurea, biuret, and dicyandiamide.
 7. A method as set forth in claim 1 in which the amylaceous material is selected from a group comprising corn flour, corn starch, grain sorghum flour, corn meal, corn grits, milo meal, milo grits, and wheat flour.
 8. A method as set forth in claim 1 in which the binder is 3.0 percent-10.0 percent of the total weight of the joint compound, and wherein the filler is 90 percent-97 percent of the total weight of the joint compound.
 9. A method as set forth in claim 3 in which the binder includes a minor percentage of polyvinyl alcohol.
 10. A method as set forth in claim 1 in which the gelatinization of the amylaceous material and the heating of the binder mixture are effected by extrusion.
 11. A wallboard joint compound comprising a mixture of a major proportion of a joint compound filler and a minor proportion of a binder wherein the binder comprises a mixture of a nitrogen compound from the family containing the chemical grouping
 12. A wallboard joint compound as claimed in claim 11 in which the amylaceous material is cereal grain or an amylaceous fraction thereof.
 13. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is urea.
 14. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is selected from a group comprising the following: urea, biurea, biuret, thiourea, guanidine, and dicyandiamide.
 15. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is of the general formula (R1R2N)2C:X, where R1 and R2 are H or CH3, and X is O or S.
 16. A wallboard joint compound as claimed in claim 11 in which the nitrogen compound is of the family containing the chemical grouping
 17. A wallboard joint compound as claimed in claim 11 in which the amylaceous material is selected from the group comprising the following: corn flour, corn starch, grain sorghum flour, corn meal, corn grits, milo meal, milo grits, and wheat flour.
 18. A wallboard joint compound as claimed in claim 11 in which the filler is 90 percent-97 percent of the total weight of the joint compound, and in which the binder is 3 percent-10 percent of the total weight of the joint compound.
 19. A wallboard joint compound as claimed in claim 11 in which the binder includes a minor percentage of polyvinyl alcohol. 